title: Engineering chiral polyoxometalate hybrid metal-organic frameworks for asymmetric dihydroxylation of olefins.
abstract: Chiral metal-organic frameworks (MOFs) with porous and tunable natures have made them feasible for performing a variety of chemical reactions as heterogeneous asymmetric catalysts. By incorporating the oxidation catalyst [BW12O40](5-) and the chiral group, L- or D-pyrrolidin-2-ylimidazole (PYI), into one single framework, the two enantiomorphs Ni-PYI1 and Ni-PYI2 were obtained via self-assembly, respectively. The channels of Ni-PYIs were enlarged through a guest exchange reaction to remove the cationic chiral templates and were well modulated with hydrophilic/hydrophobic properties to allow molecules of both H2O2 and olefin ingress and egress. The coexistence of both the chiral directors and the oxidants within a confined space provided a special environment for the formation of reaction intermediates in a stereoselective fashion with high selectivity. The resulting MOF acted as an amphipathic catalyst to prompt the asymmetric dihydroxylation of aryl olefins with excellent stereoselectivity.
authors.affiliation: State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, People's Republic of China.
authors.forename: Qiuxia
authors.initials: Q
authors.lastname: Han
authors.forename: Cheng
authors.initials: C
authors.lastname: He
authors.forename: Min
authors.initials: M
authors.lastname: Zhao
authors.forename: Bo
authors.initials: B
authors.lastname: Qi
authors.forename: Jingyang
authors.initials: J
authors.lastname: Niu
authors.forename: Chunying
authors.initials: C
authors.lastname: Duan
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D006900:Hydroxylation; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D017973:Tungsten Compounds / Q000737:chemistry*; D000099294:Polyoxometalates
chemical_list: D000475:Alkenes; D009942:Organometallic Compounds; D017973:Tungsten Compounds; C102296:polyoxometalate I; D000099294:Polyoxometalates